WO2020203957A1 - 化粧シート及びこれを用いた化粧材、並びに表面保護層用樹脂組成物 - Google Patents
化粧シート及びこれを用いた化粧材、並びに表面保護層用樹脂組成物 Download PDFInfo
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- WO2020203957A1 WO2020203957A1 PCT/JP2020/014501 JP2020014501W WO2020203957A1 WO 2020203957 A1 WO2020203957 A1 WO 2020203957A1 JP 2020014501 W JP2020014501 W JP 2020014501W WO 2020203957 A1 WO2020203957 A1 WO 2020203957A1
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- VVBVFVRWEMORTQ-UHFFFAOYSA-N CCCCC(CC)C(OCCOc(cc1O)ccc1-c1nc(-c2ccccc2)nc(-c2ccccc2)n1)=O Chemical compound CCCCC(CC)C(OCCOc(cc1O)ccc1-c1nc(-c2ccccc2)nc(-c2ccccc2)n1)=O VVBVFVRWEMORTQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- B32B2605/003—Interior finishings
Definitions
- the present invention relates to a decorative sheet, a decorative material using the decorative sheet, and a resin composition for a surface protective layer.
- decorative sheets have been used to decorate or protect the surfaces of interior and exterior members of buildings, interior and exterior members of vehicles such as automobiles, furniture, building members, home appliances, etc. ing.
- the decorative sheet has, for example, a configuration having a surface protective layer on the base material layer.
- Benzophenone-based UV absorbers and benzotriazole-based UV absorbers have been used as UV absorbers, but these have not always been satisfactory in terms of performance. Specifically, if sufficient weather resistance is to be obtained with a benzophenone-based UV absorber and a benzotriazole-based UV absorber, there is a problem that the amount of the UV absorber added increases and the UV absorber tends to bleed. It was. In addition, the benzophenone-based ultraviolet absorber and the benzotriazole-based ultraviolet absorber deteriorate significantly with time, and it is difficult to maintain weather resistance for a long period of time.
- the decorative sheets of Patent Documents 1 and 2 can suppress bleed-out and have good long-term weather resistance as compared with the decorative sheets using a benzophenone-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber.
- the decorative sheets of Patent Documents 1 and 2 are better at suppressing bleed-out and maintaining long-term weather resistance than the conventional decorative sheets, these performances may not be satisfied when used in a harsh environment. Yes, further improvement is requested.
- Patent Document 2 since the temperature condition in the weather resistance evaluation test of the decorative sheet is 53 ° C. or less, it can be said that high actual exposure weather resistance is not shown, and there is a concern that the practical performance of the decorative sheet may be low. Will be done.
- an acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component is used in order to improve the hydrophobic performance of the surface protective layer and impart long-term weather resistance.
- the surface protective layer may be hardened and the processability of the decorative sheet may be deteriorated. Therefore, the resin component used for the surface protective layer may be used. It seems necessary to limit. Therefore, it is desired that the decorative sheet can exhibit good long-term weather resistance even if the surface protective layer does not contain the monomer.
- an object of the present invention is to provide a decorative sheet and a decorative material capable of suppressing bleed-out and maintaining long-term weather resistance extremely well, and a resin composition for a surface protective layer.
- the present invention provides the following ⁇ 1> to ⁇ 3>.
- a decorative sheet having at least a base material layer and a surface protective layer.
- the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin is 10 parts by mass or less.
- the ultraviolet absorber contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (II).
- the ultraviolet absorber contains a hydroxyphenyltriazine compound represented by the following general formula (I) and a hydroxyphenyltriazine compound represented by the following general formula (III).
- Resin composition for The content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the resin composition for the surface protective layer is 10 parts by mass or less.
- a decorative sheet and a decorative material capable of suppressing bleed-out and maintaining long-term weather resistance extremely well, and a resin composition for a surface protective layer.
- the decorative sheet of the present invention is a decorative sheet having at least a base material layer and a surface protective layer, and the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the surface protective layer is 10 parts by mass or less, and the surface is protected.
- the layer satisfies the following [1] or [2].
- the ultraviolet absorber contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II).
- the ultraviolet absorber contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (III).
- FIG. 1 is a cross-sectional view showing a typical embodiment of the decorative sheet 100 of the present invention.
- the decorative sheet 100 of FIG. 1 has a surface protective layer 10 on the base material layer 50. Further, the decorative sheet 100 of FIG. 1 has a decorative layer 40, a transparent resin layer 30, and a primer layer 20 between the base material layer 50 and the surface protective layer 10.
- the decorative sheet of the present invention has a basic structure including a surface protective layer on the base material layer
- various forms of laminated structure can be selected according to the application, required performance, and the like.
- the decorative sheet 100 has the following laminated structure (1), and specific examples of other laminated structures include the following (2) to (7).
- "/" means the interface of each layer.
- the embodiment of each layer will be described later.
- Base material layer 50 / decorative layer 40 / transparent resin layer 30 / primer layer 20 / surface protective layer 10 (2) Base material layer 50 / surface protection layer 10 (3) Base material layer 50 / primer layer 20 / surface protection layer 10 (4) Base material layer 50 / transparent resin layer 30 / surface protective layer 10 (5) Base material layer 50 / decorative layer 40 / surface protective layer 10 (6) Base material layer 50 / transparent resin layer 30 / decorative layer 40 / surface protective layer 10 (7) Base material layer 50 / transparent resin layer 30 / decorative layer 40 / primer layer 20 / surface protective layer 10 In addition, in the above (1) to (7), an adhesive layer (adhesive layer A described later) may be interposed between the base material layer and the surface protection.
- the surfaces of the base material layer, the transparent resin layer, and the like can be embossed, which will be described later, to form uneven shapes such as wood grain conduit grooves, sand grain, satin finish, hairline, and skin squeezing (kawashibo).
- the hydroxyphenyltriazine compounds represented by the general formula (I), the general formula (II), and the general formula (III) are used as an ultraviolet absorber.
- the decorative sheet contains, at least, in the surface protective layer, the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III).
- the surface protective layer of the decorative sheet does not contain the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III)
- long-term weather resistance Cannot be maintained very well.
- the surface protective layer is composed of the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (III). It is more preferable to include a combination.
- the three types of hydroxyphenyltriazine compounds represented by the above general formula (I), the above general formula (II) and the above general formula (III) can be used in combination as long as the effects of the present invention are not impaired. It is difficult to obtain the effects of bleed-out suppression and long-term weather resistance that exceed the combination of the two types of compounds.
- the decorative sheet may have one or more layers selected from a decorative layer, a transparent resin layer, and a primer layer between the base material layer and the surface protective layer. Further, at least one of the base material layer, the transparent resin layer and the primer layer may contain at least one of the hydroxyphenyltriazine compounds represented by the above general formulas (I) to (III). The hydroxyphenyltriazine compound represented by the general formula (I) and the general formula (II) or the general formula (III) are added to at least one of the base material layer, the transparent resin layer and the primer layer, and the surface protective layer. The configuration containing the hydroxyphenyltriazine compound shown in the above can easily improve the long-term weather resistance of the entire decorative sheet.
- the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyl represented by the general formula (II) or the general formula (III) are added to the surface protective layer. Even if the amount added with the triazine compound is small, the long-term weather resistance of the entire decorative sheet can be easily improved.
- the general formula (II) is based on 100% by mass of the total content of the hydroxyphenyltriazine compound represented by the general formula (I) and the content of the hydroxyphenyltriazine compound represented by the general formula (II).
- the content of the hydroxyphenyltriazine compound shown in 1 is 50% by mass or less. If the content of the hydroxyphenyltriazine compound represented by the general formula (II) exceeds 50% by mass, the suppression of bleed-out is inferior and it becomes difficult to realize long-term weather resistance.
- the content of the hydroxyphenyltriazine compound represented by the general formula (II) suppresses bleed-out with respect to the total content of the hydroxyphenyltriazine compound represented by the general formula (I) and the above general formula (II) of 100% by mass.
- the content is preferably 45% by mass or less, more preferably 40% by mass or less.
- the lower limit of the content of the hydroxyphenyltriazine compound represented by the general formula (II) is not particularly limited as long as it can exhibit long-term weather resistance, but from the viewpoint that extremely good long-term weather resistance is likely to be exhibited. 1, 1% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is further preferable.
- the general formula (III) is based on 100% by mass of the total content of the hydroxyphenyltriazine compound represented by the general formula (I) and the content of the hydroxyphenyltriazine compound represented by the general formula (III) in the surface protective layer.
- the content of the hydroxyphenyltriazine compound shown in) is not particularly limited as long as it can suppress bleed-out and exhibit long-term weather resistance, but it is 95% by mass from the viewpoint that long-term weather resistance can be more easily enhanced. It is preferably less than or equal to 90% by mass or less.
- the lower limit of the content of the hydroxyphenyltriazine compound represented by the general formula (III) is not particularly limited as long as it can suppress bleed-out and exhibit long-term weather resistance, but it is likely to exhibit long-term weather resistance. From the viewpoint, 1% by mass or more is preferable, 5% by mass or more is more preferable, and 10% by mass or more is further preferable.
- the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine represented by the general formula (II) or the general formula (III) are formed on at least one of the base material layer, the transparent resin layer and the primer layer.
- total content of the compound is the thickness of the layer to which the compound is added and the layer to which the compound is added.
- the primer layer contains the hydroxyphenyltriazine compound represented by the general formula (I), the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III), and the binder resin
- the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the binder resin of the primer layer.
- the transparent resin layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III) and the binder resin, the compound.
- the total content is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the binder resin of the transparent resin layer.
- the base material layer contains the hydroxyphenyltriazine compound represented by the general formula (I), the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III), and the binder resin, the total of the compounds.
- the content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the binder resin of the base material layer.
- the cosmetic sheet of the present invention contains an ultraviolet absorber other than the hydroxyphenyltriazine compounds represented by the general formula (I), the general formula (II) and the general formula (III) as long as the effects of the present invention are not impaired. You may be doing it.
- the total content of the hydroxyphenyltriazine compounds represented by the general formula (III) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. ..
- the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin is 10 parts by mass or less. If the content exceeds 10 parts by mass, the suppression of bleed-out is inferior, and it becomes difficult to realize long-term weather resistance.
- the content of the total UV absorber in the surface protective layer with respect to 100 parts by mass of the resin is preferably 9 parts by mass or less, more preferably 8 parts by mass or less, and 7 parts by mass from the viewpoint of suppressing bleed-out and further enhancing long-term weather resistance. The following is more preferable.
- the lower limit of the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the surface protective layer is not particularly limited as long as it can exhibit long-term weather resistance, but from the viewpoint that extremely good long-term weather resistance is likely to be exhibited. , 0.01 part by mass or more is preferable, 0.1 part by mass or more is more preferable, and 0.5 part by mass or more is further preferable.
- the "total ultraviolet absorber" in the surface protective layer is contained in the surface protective layer containing the hydroxyphenyltriazine compounds represented by the general formula (I), the general formula (II) and the general formula (III). Shows all UV absorbers that are used.
- ⁇ Base layer> Examples of the base material layer include films, sheets and boards made of various types of paper, plastics, metals, woven fabrics, non-woven fabrics, wood and ceramic materials.
- a flat base material layer having a predetermined thickness is referred to as a film, a sheet, and a plate in ascending order of thickness.
- these names are treated as if they are not particularly different even if they are replaced with each other as appropriate. Further, the difference in the names (difference in thickness) does not cause a difference in the interpretation of the claims of the present invention.
- a plastic film shall include a plastic film, a sheet and a plate.
- a plastic film that can improve the handleability of the decorative sheet as a whole is preferable.
- plastics generally do not have sufficient weather resistance
- the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine represented by the general formula (II) or the general formula (III) are contained in a decorative sheet. By including the compound, the weather resistance of the plastic film as the base material layer can be improved.
- the resin constituting the plastic include olefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, polyvinyl alcohols, vinyl resins such as ethylene-vinyl alcohol copolymers, polyethylene terephthalates, and polybutylene terephthalates.
- olefin resins such as polyethylene and polypropylene
- vinyl chloride resins vinylidene chloride resins
- polyvinyl alcohols vinyl resins such as ethylene-vinyl alcohol copolymers
- polyethylene terephthalates polybutylene terephthalates
- polyester polymethyl methacrylate, methyl polyacrylate, acrylic resin such as polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate and the like can be mentioned.
- ABS resin acrylonitrile-butadiene-styren
- olefin resins one or more selected from olefin resins, vinyl chloride resins, polyesters and acrylic resins are preferable from the viewpoints of weather resistance, water resistance, printability, molding processability, price and the like.
- polypropylene-based resins and polyvinyl chloride resins are suitable because they can easily keep the moisture permeability of the decorative sheet within a predetermined range, and thus can easily improve long-term adhesion as well as construction suitability.
- the olefin resin is preferable in that the effect of the present invention can be more easily exhibited.
- the hydroxyphenyltriazine compound represented by the general formula (I) has a property of being difficult to bleed out. Therefore, the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III), which have different spectral absorption spectra while taking advantage of this property, should be used in combination. As a result, it is possible to easily absorb ultraviolet rays in the wavelength region that contributes to the deterioration of the olefin resin, and to maintain long-term weather resistance.
- the polypropylene-based resin may be a homopolymer of propylene, that is, polypropylene, or propylene and another comonomer copolymerizable with propylene (for example, ethylene, 1-butene, 1-hexene, 1-octene, etc.).
- ⁇ -Olefin; vinyl acetate, vinyl alcohol, etc. may be a copolymer.
- the moisture permeability can be adjusted by adjusting the crystallinity.
- the higher the crystallinity the lower the moisture permeability of the polypropylene resin.
- the thickness of the base material is about 40 ⁇ m or more and 200 ⁇ m or less
- the crystallinity is preferably 30% or more, more preferably 40% or more
- the upper limit is preferably 80% or less, more preferably 70% or less.
- the moisture permeability of the base material can be adjusted by adjusting the mass ratio of the isotactic polypropylene and the atactic polypropylene.
- the moisture permeability of the base material can be reduced by adding the isotactic polypropylene as compared with the case where the ratio of the atactic polypropylene in the polypropylene is 100% by mass.
- the mass ratio of the atactic polypropylene to the isotactic polypropylene is preferably 0/100 to 20/80 in consideration of the ease of adjusting the moisture permeability.
- the vinyl chloride resin a homopolymer of a vinyl chloride monomer, that is, a polyvinyl chloride or a copolymer obtained by copolymerizing a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer is also used. be able to.
- Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acids such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; butyl malate and Maleic acid esters such as diethyl malate; Fumaric acid esters such as dibutyl fumarate and diethyl fumarate; Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; Vinyl cyanide such as acrylonitrile and methacrylonitrile Olefins such as ethylene, propylene, butylene and styrene; Dienes such as isoprene and butadiene; Vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; Allyl phthalates such as diallylphthalate. , Etc
- the average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, still more preferably 1000 to 3800, from the viewpoint of easily keeping the moisture permeability within a predetermined range and improving the long-term adhesion as well as the workability. ..
- the average degree of polymerization is within the above range, excellent mechanical strength and moldability can also be obtained.
- the average degree of polymerization is the average degree of polymerization measured in accordance with JIS K6721.
- a plasticizer may be added from the viewpoint of easily keeping the moisture permeability within a predetermined range, improving the long-term adhesion as well as the workability, and improving the workability. preferable.
- the plasticizer is not particularly limited as long as it is compatible with vinyl chloride resin.
- dibutyl phthalate (DBP) dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP).
- Diundesyl phthalate (DUP) and other phthalate plasticizers Diundesyl phthalate (DUP) and other phthalate plasticizers; dibutyl adipate and other adipic acid plasticizers; tributyl phosphate, tricredyl phosphate, triphenyl phosphate and other phosphoric acid plasticizers; trimellitic acid Trimeritic acid-based plasticizers such as tributyl and trioctyl trimellitic acid; various known polyester-based plasticizers such as adipic acid-based polyester; citric acid esters such as acetyltributylcitrate and acetyltrioctylcitrate; and the like can be mentioned.
- DUP Diundesyl phthalate
- dibutyl adipate and other adipic acid plasticizers dibutyl adipate and other adipic acid plasticizers
- tributyl phosphate tricredyl
- phthalic acid-based plasticizers phthalic acid-based plasticizers, adipic acid-based plasticizers, and polyester-based plasticizers are preferable from the viewpoint of improving the long-term adhesion as well as the workability and the ease of keeping the moisture permeability within the above range.
- Phthalic acid-based plasticizers and polyester-based plasticizers are more preferable.
- these plasticizers may be used alone or in combination of two or more.
- the content of the plasticizer may be appropriately adjusted and used according to the desired moisture permeability. Although it cannot be said unconditionally, the moisture permeability of the vinyl chloride resin tends to increase as the amount of the plasticizer additive is increased.
- the content of the plasticizer is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, based on 100 parts by mass of the vinyl chloride resin. It is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 35 parts by mass or less.
- the content of the plasticizer By setting the content of the plasticizer within the above range, it becomes easy to adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the construction suitability. Further, when the content of the plasticizer is 20 parts by mass or more, the vinyl chloride resin can be made flexible and the workability can be improved, while when it is 50 parts by mass or less, the bleed-out of the plasticizer is suppressed. , It becomes easy to stably adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the construction suitability.
- the content thereof is relative to 100 parts by mass of the vinyl chloride resin. It is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass. It is as follows.
- polyester plasticizer When a polyester plasticizer is used, its content is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin.
- the upper limit is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 25 parts by mass or less.
- the base material is composed of only a resin selected from a polypropylene resin and a polyvinyl chloride resin, but other resins may be contained.
- resins containing polyolefins such as polyethylene (low density, medium density, high density), polymethylpentene, polybutene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and the like are preferable, and polyethylene (polyethylene (low density, medium density, high density)) is preferable. Low density, medium density, high density) is more preferable.
- the base material layer may be colorless and transparent, or may be colored from the viewpoint of designability.
- a colorant such as a dye and a pigment can be added to the base material layer.
- pigments that easily suppress fading are preferable.
- white pigments such as zinc flower, lead white, lithopon, titanium dioxide (titanium white), precipitated barium sulfate and barite
- black pigments such as carbon black, aometinazo black pigment, perylene black pigment
- lead tan Red pigments such as iron oxide red, quinacridone red, polyazo red
- yellow pigments such as yellow lead, zinc yellow (1 zinc yellow, 2 zinc yellow), isoindolinone yellow, nickel-azo complex
- ultramarine blue, prussian blue Blue pigments such as (ferroic iron potassium); etc.
- the thickness of the base material layer is not particularly limited, but when the base material layer is a plastic film, it is preferably 20 to 3200 ⁇ m, more preferably 40 to 200 ⁇ m, further preferably 40 to 160 ⁇ m, and even more preferably 40 to 100 ⁇ m.
- the substrate layer is paper, the basis weight, usually preferably 20 ⁇ 150g / m 2, more preferably 30 ⁇ 100g / m 2.
- the shape of the base material layer is not limited to a flat plate shape, and may be a special shape such as a three-dimensional shape.
- one or both sides of the base material layer may be subjected to a physical surface treatment such as an oxidation method or an unevenness method, or a chemical surface. Surface treatment such as treatment may be performed, or a primer layer may be formed.
- the surface protective layer preferably contains a cured product of the curable resin composition from the viewpoint of improving the scratch resistance of the decorative sheet.
- the cured product of the curable resin composition is a resin component contained in the surface protective layer.
- the surface protective layer contains components other than the resin component (for example, the hydroxyphenyltriazine compounds represented by the above general formulas (I) to (III)), and the cured product of the curable resin composition has a role as a binder resin. ..
- the ratio of the cured product of the curable resin composition to the total resin components constituting the surface protective layer is preferably 70% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. It is more preferably 100% by mass, and even more preferably 100% by mass.
- the resin composition for the surface protective layer forming the surface protective layer examples include the curable resin composition, the hydroxyphenyltriazine compound represented by the general formula (I), and the general formula (II) or the general formula (III).
- the resin composition for the surface protective layer includes the curable resin composition, the hydroxyphenyltriazine compound represented by the general formula (I), and the hydroxy represented by the general formula (II) or the general formula (III).
- the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the resin composition for the surface protective layer is 10 parts by mass or less. It is preferable to satisfy the following [1] or [2].
- the ultraviolet absorber contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II). Hydroxyphenyltriazine represented by the general formula (II) with respect to a total of 100% by mass of the content of the hydroxyphenyltriazine compound represented by the general formula (I) and the content of the hydroxyphenyltriazine compound represented by the general formula (II). The content of the compound is 50% by mass or less.
- the ultraviolet absorber contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (III).
- the preferred embodiment of the total ultraviolet absorber content with respect to 100 parts by mass of the resin in the resin composition for the surface protective layer is the same as the preferred embodiment of the total ultraviolet absorber content with respect to 100 parts by mass of the resin in the surface protective layer described above. Is. Further, the content of the hydroxyphenyltriazine compound represented by the general formula (I) of the above [1] and [2] in the resin composition for the surface protective layer and the hydroxyphenyltriazine represented by the general formula (II) or the general formula (III).
- the content of the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine represented by the general formula (II) or the general formula (III) in the above-mentioned surface protective layer This is similar to the preferred embodiment of the ratio to the content of the compound.
- the other additives that can be contained in the resin composition for the surface protective layer are the same as the other additives that can be contained in the surface protective layer described later.
- the curable resin composition examples include a thermosetting resin composition containing a thermosetting resin, an ionizing radiation curable resin composition containing an ionizing radiation curable resin, and a mixture thereof.
- an ionizing radiation curable resin composition is preferable from the viewpoint of increasing the crosslink density of the surface protective layer and improving the surface characteristics such as scratch resistance.
- the electron beam curable resin composition is more preferable among the ionizing radiation curable resin compositions from the viewpoint that it can be applied without a solvent and is easy to handle. Further, it is preferable that the curable resin composition does not contain cyclohexyl (meth) acrylate as a monomer component.
- the surface protective layer preferably does not contain a cured product of cyclohexyl (meth) acrylate.
- the curable resin composition contains cyclohexyl (meth) acrylate as a monomer component, the surface protective layer may become hard and the processability of the decorative sheet may decrease, which is inconvenient for the use of the decorative material having the decorative sheet. It is possible that it may occur.
- the thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
- the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.
- a curing agent is added to these curable resins as needed.
- the ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”).
- the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group is preferable.
- a (meth) acryloyl group means an acryloyl group or a metachloroyl group.
- (meth) acrylate means acrylate or methacrylate.
- ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and ⁇ -rays, and charged particle beams such as ⁇ -rays and ion rays are also included.
- the ionizing radiation curable compound can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.
- a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
- “(meth) acrylate” means "acrylate or methacrylate”.
- Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.
- the number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, and further preferably 2 or more and 4 or less. More preferably 2 or more and 3 or less.
- These polyfunctional (meth) acrylates may be used alone or in combination of two or more.
- polymerizable oligomer examples include (meth) acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional groups.
- urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, acrylic (meth) acrylate oligomer and the like can be mentioned.
- polymerizable oligomer a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group on the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond on the main chain.
- aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, novolak type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.
- oligomers and the like having cationically polymerizable functional groups.
- polymerizable oligomers may be used alone or in combination of two or more. From the viewpoint of improving processing properties, scratch resistance and weather resistance, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate One or more selected from oligomers and acrylic (meth) acrylate oligomers is preferable, one or more selected from urethane (meth) acrylate oligomers and polycarbonate (meth) acrylate oligomers is more preferable, and urethane (meth) acrylate oligomers are even more preferable. ..
- the surface protective layer preferably contains a cured product of urethane (meth) acrylate oligomer.
- the ratio of the cured product of the urethane (meth) acrylate oligomer to the total amount of the resin component contained in the surface protective layer is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass. The above is more preferable, and 100% by mass is even more preferable.
- Urethane (meth) acrylate oligomers are obtained, for example, by reacting polyols and organic diisocyanates with hydroxy (meth) acrylates.
- the urethane (meth) acrylate oligomer preferably has 1 to 6 carbon atoms of the alkylene group derived from the polyol as a raw material, and more preferably 2 to 4 carbon atoms.
- the number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, more preferably 6 or less, still more preferably 4 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. 3 or less is even more preferable.
- the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, and more preferably 3,000 or more and 7,000 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. , 3,500 or more and 6,000 or less are more preferable.
- the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.
- a monofunctional (meth) acrylate can be used in combination with the ionizing radiation curable resin composition for the purpose of reducing the viscosity of the ionizing radiation curable resin composition.
- These monofunctional (meth) acrylates may be used alone or in combination of two or more.
- the composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator.
- a photopolymerization initiator include one or more selected from acetophenone, benzophenone, ⁇ -hydroxyalkylphenone, Michler ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, ⁇ -acyl oxime ester, thioxanthones and the like.
- the photopolymerization accelerator can reduce the polymerization inhibition by air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.
- the surface protective layer contains the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III).
- the surface protective layer also preferably contains other additives such as antioxidants and light stabilizers.
- the thickness of the surface protective layer is preferably 1.5 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less, and further preferably 3 ⁇ m or more and 10 ⁇ m or less from the viewpoint of the balance between processing characteristics, scratch resistance and weather resistance.
- the decorative sheet preferably has a primer layer in contact with the surface of the surface protective layer on the base material layer side.
- the primer layer improves the adhesion between the base material layer and the surface protective layer (in the case of having a transparent resin layer, the adhesion between the transparent resin layer and the surface protective layer), and is used for a long period of time when exposed outdoors. It is possible to easily secure interlayer adhesion (so-called weather resistance) and improve scratch resistance.
- the primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.
- the ultraviolet absorber of the primer layer is preferably a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III).
- urethane resin acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (in the polymer main chain).
- the binder resin may be one obtained by cross-linking and curing these resins by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent.
- a polyol resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate-based curing agent, and a acrylic polyol resin is more preferably crosslinked and cured with an isocyanate-based curing agent.
- the thickness of the primer layer is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 2 ⁇ m or more and 8 ⁇ m or less, and further preferably 3 ⁇ m or more and 6 ⁇ m or less.
- the decorative sheet may have a back surface primer layer on the opposite side of the base material layer to the front surface protective layer for the purpose of improving the adhesiveness with the adherend.
- the decorative sheet may have a transparent resin layer between the base material layer and the surface protective layer from the viewpoint of increasing the strength.
- the transparent resin layer is preferably located between the base material layer and the primer layer.
- the transparent resin layer is preferably located between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer.
- the resin constituting the transparent resin layer examples include polyolefin-based resin, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), acrylic resin, vinyl chloride resin and the like.
- ABS resin acrylonitrile-butadiene-styrene resin
- acrylic resin vinyl chloride resin
- the transparent resin layer may be a mixture of these exemplified resins, or may be a laminate of one or more layers of these exemplified resins.
- polypropylene and polyvinyl chloride resin are preferable because the moisture permeability of the decorative sheet is kept within a predetermined range, and it is easy to improve the long-term adhesion as well as the workability.
- the content of the polyolefin resin in the transparent resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total resin components of the transparent resin layer. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
- the polyolefin-based resin of the transparent resin layer includes polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-vinyl acetate.
- examples thereof include polymers, ethylene-acrylic acid copolymers, and ethylene-propylene-butene copolymers.
- polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferable, and polypropylene is more preferable.
- polypropylene and polyvinyl chloride resins preferable from the viewpoint of moisture permeability include those similar to those exemplified for the base material.
- the transparent resin layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant.
- the ultraviolet absorber includes the hydroxyphenyltriazine compound represented by the general formula (I) and the hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III). Is preferable.
- the thickness of the transparent resin layer is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 40 ⁇ m or more and 120 ⁇ m or less, and further preferably 60 ⁇ m or more and 100 ⁇ m or less, from the viewpoint of the balance between scratch resistance, processing suitability and weather resistance.
- the decorative sheet preferably has a decorative layer at any position on the decorative sheet.
- the portion where the decorative layer is formed is preferably on the side close to the base material layer from the viewpoint of enhancing the weather resistance of the decorative layer.
- the decorative layer is preferably located between the base material layer and the primer layer.
- the decorative layer is preferably located between the base material layer and the transparent resin layer.
- the decorative layer may be, for example, a colored layer that covers the entire surface (so-called solid colored layer), or may be a pattern layer formed by printing various patterns using ink and a printing machine. Good.
- the patterns of the pattern layer include wood grain patterns such as annual rings and conduit grooves on the surface of the wood board, stone grain patterns on the stone plate surface such as marble and granite, cloth grain patterns on the cloth surface, leather grain patterns on the leather surface, and geometry. It may be a pattern, a character, a figure, or a combination thereof.
- the ink used for the decorative layer is a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like.
- a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like.
- the binder resin for the decorative layer is not particularly limited, and for example, urethane resin, acrylic polyol, acrylic resin, polyester, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer, etc.
- Examples thereof include vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.
- the colorant a pigment having excellent hiding power and weather resistance is preferable.
- the same pigment as those exemplified in the base material layer can be used.
- the content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. The following is more preferable.
- the decorative layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant.
- the ultraviolet absorber is a hydroxyphenyltriazine compound represented by the general formula (I) and a hydroxyphenyltriazine compound represented by the general formula (II) or the general formula (III). Is preferable.
- the thickness of the decorative layer may be appropriately selected according to the desired pattern, but from the viewpoint of hiding the ground color of the adherend and improving the design, it is preferably 0.5 ⁇ m or more and 20 ⁇ m or less, and 1 ⁇ m or more and 10 ⁇ m. The following is more preferable, and 2 ⁇ m or more and 5 ⁇ m or less is further preferable.
- the decorative sheet has a transparent resin layer
- a decorative layer is further provided between the base material layer and the transparent resin layer
- the positional relationship between the adhesive layer A and the decorative layer is not particularly limited.
- the decorative layer, the adhesive layer A and the transparent resin layer may be provided in this order from the side closer to the base material layer, or the adhesive layer A, the decorative layer A and the transparent resin layer may be provided from the side closer to the base material layer.
- the transparent resin layer may be provided in this order.
- the adhesive layer A can be composed of, for example, a general-purpose adhesive such as a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, or a rubber-based adhesive.
- a general-purpose adhesive such as a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, or a rubber-based adhesive.
- urethane-based adhesives are preferable in terms of adhesive strength.
- the urethane-based adhesive include an adhesive using a two-component curable urethane resin containing various polyol compounds such as a polyether polyol, a polyester polyol, and an acrylic polyol, and a curing agent such as an isocyanate compound.
- the thickness of the adhesive layer A is preferably 0.1 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 15 ⁇ m or less, and further preferably 2 ⁇ m or more and 10 ⁇ m or less.
- the above-mentioned decorative layer, adhesive layer A, primer layer and surface protective layer are coated with a coating liquid containing a composition forming each layer by a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. It can be formed by applying it by a known method such as, and if necessary, drying and curing it. Further, the transparent resin layer can be formed by, for example, heat melt extrusion.
- the decorative sheet may be given a desired uneven shape (also referred to as an uneven pattern) (also referred to as shaping) by embossing or the like.
- embossing for example, the decorative sheet is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 160 ° C. or lower, and further preferably 100 ° C. or higher and 140 ° C. or lower, and the embossing plate is pressed against the decorative sheet. Then, embossing can be performed.
- the portion where the embossed plate is pressed is preferably on the surface protective layer side of the decorative sheet.
- Decorative sheet of the present invention preferably has a moisture permeability is not more than 0.75g / m 2 ⁇ 24h or more 45g / m 2 ⁇ 24h.
- moisture permeability is not more than 0.75g / m 2 ⁇ 24h or more 45g / m 2 ⁇ 24h.
- it is further excellent in construction suitability, long-term adhesion, process suitability, and weather resistance (particularly, suppression of appearance change when exposed to ultraviolet rays in sunlight).
- the initial adhesion strength in the construction process is improved, so that the end face of the decorative sheet is peeled off due to insufficient initial adhesion strength during construction. Since the occurrence of so-called springback can be suppressed, the construction efficiency is improved.
- the effect of improving the initial adhesion strength is particularly remarkable when the decorative sheet is attached to the adherend via a moisture-curable and hot-melt type urethane resin-based adhesive layer that requires moisture at the time of initial adhesion. It is played by.
- the decorative sheet and the adherend are used as the decorative material via the adhesive layer, the deterioration of the adhesive layer between the decorative sheet and the adherend can be suppressed mainly due to the deterioration. Peeling is suppressed, peeling does not occur even after long-term use, and long-term adhesion is improved.
- the moisture permeability of the decorative sheet within the above range, it is possible to improve the construction suitability by improving the initial adhesion strength in the construction process and to improve the long-term adhesion that does not cause peeling even after long-term use.
- the effect of improving the long-term adhesion strength is particularly obtained by using a decorative sheet as an adherend via a urethane resin-based adhesive layer such as a moisture-curable and hot-melt type urethane resin, which has a property of being deteriorated by hydrolysis due to moisture. It is noticeably played when it is attached.
- the effect of long-term adhesion by setting the moisture permeability within the above range is that the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the surface protective layer is 10 parts by mass or less, and the surface protective layer is the above. It is obtained by satisfying [1] or [2].
- the surface protective layer does not have the above-mentioned structure, even if the moisture permeability is in the above range, the base material and the adhesive layer are affected by the action of ultraviolet rays due to the breakage of the molecular chain of the resin or the photochemical reaction. It deteriorates, which causes a decrease in mechanical strength in the vicinity of the adhesive interface and an increase in moisture permeability of the decorative sheet, so that long-term adhesion cannot be improved.
- the configuration of the surface protective layer as was optimized as described above if the moisture permeability of the decorative sheet is more than 45g / m 2 ⁇ 24h, besides decrease in the long-term adhesion, weather resistance on the change in the appearance Is also likely to decline.
- the reasons for this are "as the moisture permeability of the decorative sheet increases, the permeability of the UV absorber contained in the decorative sheet also increases, so that the UV absorber tends to bleed out" and "for a long period of time.” It is considered that the amount of reduction of the ultraviolet absorber in the decorative sheet increases with outdoor exposure, and the durability of the decorative sheet to ultraviolet rays gradually decreases.
- the moisture permeability is less than 45g / m 2 ⁇ 24h
- the adhesive used on the adhesive layer Since deterioration due to hydrolysis can be suppressed, peeling between the decorative sheet and the adherend is less likely to occur, and long-term adhesion that does not cause peeling even after long-term use is improved. Therefore, by setting the moisture permeability of the decorative sheet within the above range, it is possible to simultaneously improve the construction suitability due to the high initial adhesion strength in the construction process and the long-term adhesion that does not cause peeling even after long-term use.
- moisture permeability 1.2g / m 2 ⁇ 24h or more, more preferably 1.5g / m 2 ⁇ 24h, more preferably 2.5g / m 2 ⁇ 24h or more , even more preferably at 4.5g / m 2 ⁇ 24h or more, preferably 40g / m 2 ⁇ 24h or less as the upper limit, more preferably 35g / m 2 ⁇ 24h or less, even more preferably not more than 30g / m 2 ⁇ 24h , even more preferably at most 20g / m 2 ⁇ 24h.
- the moisture permeability can be adjusted mainly by the type of the material constituting the base material, and when having the resin resin layer, the type of the material constituting the resin layer and the like.
- the decorative material of the present invention has an adherend and the above-mentioned decorative sheet of the present invention. Specifically, a surface requiring decoration of the adherend and a surface of the decorative sheet on the base material layer side. Are laminated so as to face each other.
- adherend examples include plate materials such as flat plates and curved plates made of various materials described later; three-dimensional articles such as cylinders and polygonal prisms made of various materials described later; sheets and films made of various materials described later.
- Various materials include wood single boards made of various woods such as cedar, cypress, pine, and lauan, wood plywood, laminated wood, particle boards, and wood members such as MDF (medium density fiberboard); iron, Metal members such as aluminum, copper, or alloys containing one or more of these metals; ceramics such as glass and ceramics, ceramics such as gypsum, cement, ALC (lightweight cellular concrete), and non-ceramic ceramic materials such as calcium silicate.
- Acrylic resin polyolefin resin such as polyester, polystyrene and polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, resin member such as rubber and the like can be mentioned.
- these materials can be used alone or in combination of two or more.
- the adherend may be appropriately selected from the above depending on the application.
- the adherend is made of at least one member selected from the resin members.
- the adherend is made of at least one member selected from a metal member and a resin member.
- the thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm or more and 100 mm or less, more preferably 0.3 mm or more and 5 mm or less, and further preferably 0.5 mm or more and 3 mm or less.
- ⁇ Adhesive layer B> The adherend and the decorative sheet are preferably bonded to each other via the adhesive layer B in order to obtain excellent adhesiveness.
- the adhesive constituting the adhesive layer B is not particularly limited, and a known adhesive can be used.
- a moisture-curable adhesive, an anaerobic curable adhesive, a dry-curable adhesive, and a UV-curable adhesive can be used.
- Adhesives such as mold adhesives, heat sensitive adhesives (for example, hot melt type adhesives), and pressure sensitive adhesives are preferable.
- a moisture-curable adhesive and a heat-sensitive adhesive are preferable in consideration of compatibility with the decorative sheet of the present embodiment having a predetermined moisture permeability, ease of handling, and the like.
- the heat-sensitive adhesive is preferable in that the molten liquid adhesive layer is cooled and solidified, and at the same time, the adhesive force rises to a saturated state.
- the moisture-curable adhesive when used in combination with the decorative sheet of the present embodiment, it can be exposed to an appropriate amount of moisture in the construction process, so that the initial adhesion strength of the adhesive used for the adhesive layer can be obtained.
- the initial adhesion strength of the adhesive used for the adhesive layer can be obtained.
- it does not come into contact with excessive moisture since it does not come into contact with excessive moisture, a decrease in adhesiveness due to deterioration due to hydrolysis is suppressed, and as a result, it becomes easy to obtain better construction suitability and long-term adhesiveness. It is also preferable in terms of ease of handling.
- the adhesive constituting the adhesive layer B is selected from resins such as acrylic resin, urethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, polyester, and polyamide. Those containing one kind or two or more kinds are mentioned. Further, examples of the adhesive for the adhesive layer B include a two-component curable polyurethane-based adhesive and a polyester-based adhesive using an isocyanate compound or the like as a curing agent. Further, an adhesive may be used for the adhesive layer. As the pressure-sensitive adhesive, an acrylic-based, urethane-based, silicone-based, rubber-based, or other pressure-sensitive adhesive can be appropriately selected and used.
- a moisture-curable adhesive which is one of the adhesives preferably used in the present embodiment, and which has a urethane resin resin, contains a prepolymer having an isocyanate group at the molecular terminal as an essential component. ..
- the prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both ends of the molecule, and is in the state of a solid thermoplastic resin at room temperature.
- polyisocyanate prepolymer for example, a solid polyester polyol which is crystalline at room temperature is used as a polyol component, and a polyisocyanate composed of 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, or the like is used as a polyisocyanate component.
- a polyisocyanate composed of 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, or the like is used as a polyisocyanate component.
- the thickness of the adhesive layer B is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 50 ⁇ m or less, and further preferably 10 ⁇ m or more and 30 ⁇ m or less.
- the decorative material can be produced through a process of laminating a decorative sheet and an adherend.
- This step is a step of laminating the adherend and the decorative sheet of the present invention, in which the surface of the adherend that requires decoration and the surface of the decorative sheet on the base material layer side are opposed to each other and laminated.
- Examples of the method of laminating the adherend and the decorative sheet include a laminating method in which the decorative sheet is pressurized and laminated on the plate-shaped adherend with a pressure roller via the adhesive layer B.
- the heating temperature is preferably 160 ° C. or higher and 200 ° C. or lower, and 100 for the reactive hot melt adhesive, although it depends on the type of resin constituting the adhesive. °C or more and 130 °C or less are preferable. Further, in the case of vacuum forming, it is generally performed while heating, and it is preferably 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower.
- the decorative material obtained as described above can be arbitrarily cut, and the surface and the end of the wood can be arbitrarily decorated by grooving, chamfering, etc. using a cutting machine such as a router or a cutter.
- a cutting machine such as a router or a cutter.
- various uses for example, interior members of buildings such as walls, ceilings, floors, exterior members such as outer walls, eaves ceilings, roofs, fences, fences, window frames, doors, door frames, handrails, skirting boards, etc. It can be used for fittings and building members such as peripheral edges and moldings, as well as surface decorative boards for kitchens, furniture or home appliances, cabinets such as OA equipment, interior and exterior members of vehicles, and the like.
- a transparent polyurethane resin-based adhesive is applied onto the decorative layer to form an adhesive layer (thickness after drying: 3 ⁇ m), and the transparent polypropylene resin is heated, melted and extruded by a T-die extruder to be transparent. A sex resin layer (thickness: 80 ⁇ m) was formed.
- a coating liquid containing a resin composition containing a resin component composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol is applied by a gravure printing method to be a primer.
- a layer (thickness after drying: 4 ⁇ m) was formed.
- the following resin composition for a surface protection layer is applied onto the primer layer by a roll coating method to form an uncured resin layer, which is not irradiated with an electron beam (acceleration voltage: 175 kV, 5Mrad (50 kGy)).
- the cured resin layer was cured to form a surface protective layer (thickness: 5 ⁇ m).
- embossing was performed on the surface protective layer to prepare a decorative sheet.
- (Resin composition for surface protective layer) Hydroxy represented by the general formula (I), the general formula (II) and the general formula (III) as an ultraviolet absorber in 100 parts by mass of a trifunctional urethane acrylate oligomer (weight average molecular weight of about 5000, ionizing radiation curable compound).
- the phenyltriazine compound was added at the ratios shown in Tables 1 to 3 to prepare a resin composition for a surface protective layer.
- the following hydroxyphenyltriazine compound was used as the ultraviolet absorber.
- -Ultraviolet absorber 1 (the general formula (I)): [ADEKA STAB LA-46, manufactured by ADEKA CORPORATION]
- -Ultraviolet absorber 2 (general formula (II)): [Chinubin 479, manufactured by Ciba Specialty Chemicals Co., Ltd.]
- -Ultraviolet absorber 3 (general formula (III)): [Chinubin 1600, manufactured by Ciba Specialty Chemicals Co., Ltd.]
- the “content ratio of chinubin 479” is the content (mass%) of the ultraviolet absorber 2 with respect to the total 100% by mass of the content of the ultraviolet absorber 1 and the content of the ultraviolet absorber 2.
- the “content ratio of tinubin 1600” means the content (mass%) of the ultraviolet absorber 3 with respect to the total 100% by mass of the content of the ultraviolet absorber 1 and the content of the ultraviolet absorber 3.
- the “content ratio of chinubin 479 or 1600” is the ultraviolet absorber 2 or the ultraviolet absorber with respect to the total content of the ultraviolet absorber 1 and the content of the ultraviolet absorber 2 or the ultraviolet absorber 3 by 100% by mass. It means the content (mass%) of 3.
- the decorative sheets of Examples 1 to 14 are excellent in suppressing bleed-out and excellent in evaluation of long-term weather resistance. Therefore, the maintenance of long-term weather resistance is extremely good even when used in a harsh environment. It can be confirmed that it can be demonstrated.
- the decorative sheet of Comparative Example 1 has a large content of the total ultraviolet absorber in the surface protective layer, and the decorative sheets of Comparative Examples 2 and 3 have the hydroxyphenyl represented by the general formula (II). Due to the high content of the triazine compound, the results were inferior in both suppression of bleed-out and maintenance of long-term weather resistance.
- a peeling test was conducted using a Tencilon universal material tester (“Tencilon RTC-1250A (product name)”, manufactured by Orientec Co., Ltd.) under the conditions of tensile speed: 10 mm / min, peeling direction 90 °, and chuck distance: 30 mm. , The peeling strength was measured as the initial adhesive strength and evaluated according to the following criteria. If the evaluation is B or higher, the evaluation of construction suitability is passed. A: The peeling strength was 1.0 N / mm or more. B: The peeling strength was 0.5 N / mm or more and less than 1.0 N / mm. C: The peeling strength was less than 0.5 N / mm.
- Example 15 In Example 1, except that the base material layer was a polypropylene resin sheet (thickness: 80 ⁇ m, crystallinity: 70%, propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less)). Obtained a decorative sheet of Example 15 in the same manner as in Example 1.
- Example 16 In Example 1, except that the base material layer was a polypropylene resin sheet (thickness: 60 ⁇ m, crystallinity: 50%, propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less)). Obtained a decorative sheet of Example 16 in the same manner as in Example 1.
- Example 17 In Example 1, the base material layer was a polypropylene resin sheet (thickness: 60 ⁇ m, crystallinity: 40%, propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less)) and was transparent. A decorative sheet of Example 17 was obtained in the same manner as in Example 1 except that the thickness of the sex resin layer was 40 ⁇ m.
- Comparative Example 4 In Comparative Example 1, the base material layer was a polypropylene resin sheet (thickness: 100 ⁇ m, crystallinity: 70%, propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less)) and was transparent. A decorative sheet of Comparative Example 4 was obtained in the same manner as in Comparative Example 1 except that the thickness of the sex resin layer was 100 ⁇ m.
- the decorative sheet of the present invention is extremely good at suppressing bleed-out and maintaining long-term weather resistance, it is used for exterior members such as entrance doors, window frames, fittings such as doors, and other members used in an environment exposed to direct sunlight. It is suitably used as a decorative sheet for doors.
- Decorative sheet 10 Surface protective layer 20: Primer layer 30: Transparent resin layer 40: Decorative layer 50: Base material layer
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Abstract
Description
しかし、特許文献1及び2の化粧シートは、従来の化粧シートに比べるとブリードアウトの抑制及び長期耐候性の維持が良好であるものの、過酷な環境での使用においてはこれら性能を満足できない場合があり、さらなる改善が要望されている。
特に特許文献2では、化粧シートの耐候性評価試験における温度条件が53℃以下であることから高い実曝耐候性が示されていないといえ、化粧シートの実用性能が低いおそれがあることが懸念される。また、特許文献2の化粧シートでは、表面保護層の疎水性能を向上させて長期耐候性を付与するため、シクロヘキシル(メタ)アクリレートをモノマー成分として含有するアクリル系樹脂組成物を用いている。しかし、当該モノマー成分は表面保護層に用いられる樹脂成分との相性によっては、表面保護層を硬くしてしまい化粧シートの加工性を低下させるおそれがあるため、表面保護層に用いられる樹脂成分を制限する必要があると考えられる。そのため、表面保護層において当該モノマーを含有しなくても、化粧シートに良好な長期耐候性を発現できることが望まれる。
〈1〉少なくとも基材層及び表面保護層を有する化粧シートであって、
前記表面保護層において、樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、
前記表面保護層が次の[1]又は[2]を満たす、化粧シート。
[1]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物とを含有し、
下記一般式(I)に示すヒドロキシフェニルトリアジン化合物の含有量と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量との合計100質量%に対する、下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量が50質量%以下である。
[2]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含有する。
〈3〉硬化性樹脂組成物と、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含む、表面保護層用樹脂組成物であり、
上記表面保護層用樹脂組成物における樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、
上記[1]又は[2]を満たす、表面保護層用樹脂組成物。
本発明の化粧シートは、少なくとも基材層及び表面保護層を有する化粧シートであって、表面保護層において、樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、表面保護層が次の[1]又は[2]を満たすものである。
[1]紫外線吸収剤として上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(II)に示すヒドロキシフェニルトリアジン化合物とを含有し、
上記一般式(I)に示すヒドロキシフェニルトリアジン化合物の含有量と上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量との合計100質量%に対する、上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量が50質量%以下である。
[2]紫外線吸収剤として上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含有する。
図1の化粧シート100は、基材層50上に表面保護層10を有している。また、図1の化粧シート100は、基材層50と表面保護層10との間に、装飾層40、透明性樹脂層30及びプライマー層20を有している。
(1)基材層50/装飾層40/透明性樹脂層30/プライマー層20/表面保護層10
(2)基材層50/表面保護層10
(3)基材層50/プライマー層20/表面保護層10
(4)基材層50/透明性樹脂層30/表面保護層10
(5)基材層50/装飾層40/表面保護層10
(6)基材層50/透明性樹脂層30/装飾層40/表面保護層10
(7)基材層50/透明性樹脂層30/装飾層40/プライマー層20/表面保護層10
なお、上記(1)~(7)において、基材層と表面保護との間に接着剤層(後述する接着剤層A)を介在させることもできる。また、基材層及び透明性樹脂層等の表面に、後述するエンボス加工等により、木目導管溝、砂目、梨地、ヘアライン、皮絞(カワシボ)等の凹凸形状を賦形することもできる。
本発明において、上記一般式(I)、上記一般式(II)、及び上記一般式(III)に示すヒドロキシフェニルトリアジン化合物は紫外線吸収剤として用いられる。
上記化粧シートは、少なくとも表面保護層に、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含む。
化粧シートの表面保護層が、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含まない場合、長期耐候性の維持を極めて良好なものとすることができない。より優れたブリードアウトの抑制及び長期耐候性を発現しやすい観点から、表面保護層は、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(III)に示すヒドロキシフェニルトリアジン化合物との組合せを含むことがより好ましい。
なお、本発明の効果を損なわない限りにおいて、上記一般式(I)、上記一般式(II)及び上記一般式(III)に示す3種類のヒドロキシフェニルトリアジン化合物を併用することもできるが、上述の2種類の化合物の組み合わせを超えるブリードアウト抑制及び長期耐候性の効果は得られにくい。
また、基材層、透明性樹脂層及びプライマー層の少なくともいずれかの層には、上記一般式(I)~(III)に示すヒドロキシフェニルトリアジン化合物の少なくとも何れかが含まれていてもよい。
基材層、透明性樹脂層及びプライマー層の少なくとも何れか、並びに、表面保護層に、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含む構成とすることにより、化粧シート全体の長期耐候性を良好にしやすくできる。また、化粧シートが当該構成を有する実施形態の場合、表面保護層への上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物との添加量を少なくしても、化粧シート全体の長期耐候性を良好にしやすくできる。
上記一般式(I)及び上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量の合計100質量%に対する、上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量は、ブリードアウトの抑制及び長期耐候性をより容易に高めることができる観点から、45質量%以下であることが好ましく、40質量%以下であることがより好ましい。また、上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の該含有量の下限値は、長期耐候性を発現することができれば特に制限はないが、極めて良好な長期耐候性を発現しやすい観点から、1質量%以上が好ましく、5質量%以上がより好ましく、10質量%以上がさらに好ましい。
(2)透明性樹脂層が上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物及びバインダー樹脂を含む場合、該化合物の合計含有量は、透明性樹脂層のバインダー樹脂100質量部に対して0.5~40質量部が好ましく、1~30質量部がより好ましく、5~25質量部がさらに好ましい。
(3)基材層が上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物及びバインダー樹脂を含む場合、該化合物の合計含有量は、基材層のバインダー樹脂100質量部に対して0.1~5質量部が好ましく、0.2~3質量部がより好ましく、0.3~2質量部がさらに好ましい。
本発明の化粧シート全体に含まれる全紫外線吸収剤に対する、上記一般式(I)及び上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有割合の合計、並びに、上記一般式(I)及び上記一般式(III)に示すヒドロキシフェニルトリアジン化合物の含有割合の合計はそれぞれ、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましい。
表面保護層における樹脂100質量部に対する全紫外線吸収剤の含有量は、ブリードアウトの抑制及び長期耐候性をより高める観点から、9質量部以下が好ましく、8質量部以下がより好ましく、7質量部以下がさらに好ましい。また、表面保護層における樹脂100質量部に対する全紫外線吸収剤の含有量の下限値は、長期耐候性を発現することができれば特に制限はないが、極めて良好な長期耐候性を発現しやすい観点から、0.01質量部以上が好ましく、0.1質量部以上がより好ましく、0.5質量部以上がさらに好ましい。
なお、表面保護層における上記「全紫外線吸収剤」とは、上記一般式(I)、上記一般式(II)及び上記一般式(III)に示すヒドロキシフェニルトリアジン化合物を含む、表面保護層に含有される全ての紫外線吸収剤を示す。
基材層としては、各種の紙類、プラスチック、金属、織布、不織布、木材及び窯業系素材等からなるフィルム、シート及び板が挙げられる。
通常、所定厚みを持つ平面状の基材層は、厚みの薄い順にフィルム、シート、板と区別して呼称されるが、本発明においては厚みの相違を区別する必要性は特にないため、本明細書中に於いては、これら呼称は適宜相互に置き換えても特に本質的相違は無いものとして取り扱う。また、これら呼称の相違(厚みの相違)によって、本発明の特許請求の範囲の解釈に相違を生じるものでもない。なお、本明細書において、プラスチックフィルムとは、プラスチック製のフィルム、シート及び板を包括したものとする。
基材層の中では、化粧シート全体としての取り扱い性を良好にすることができるプラスチックフィルムが好ましい。なお、プラスチックは一般的に耐候性が十分ではないが、化粧シート中に上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含むことにより、基材層としてのプラスチックフィルムの耐候性を良好にすることができる。
これらの中でも、耐候性、耐水性、印刷適性、成形加工適性及び価格等の観点からオレフィン系樹脂、塩化ビニル樹脂、ポリエステル及びアクリル樹脂から選ばれる1種以上が好ましい。
また、ポリプロピレン系樹脂及びポリ塩化ビニル樹脂は、化粧シートの透湿度を所定の範囲内としやすくなるため、施工適性とともに長期密着性を向上させやすい点で好適である。
また、プロピレンの単独重合体(ポリプロピレン)を用いる場合、アイソタクチックポリプロピレンとアタクチックポリプロピレンとの質量比の調節により基材の透湿度を調整することもできる。一般的には、ポリプロピレン中のアタクチックポリプロピレンの割合が100質量%の場合に比べて、アイソタクチックポリプロピレンを添加することで基材の透湿度を低下させることができる。この場合、アタクチックポリプロピレンとアイソタクチックポリプロピレンとの質量比は、透湿度の調整のしやすさを考慮すると、好ましくは0/100~20/80である。
塩化ビニルモノマーと共重合可能なモノマーとしては、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類;メチルアクリレートやブチルアクリレート等のアクリル酸エステル類;メチルメタクリレートやエチルメタクリレート等のメタクリル酸エステル類;ブチルマレートやジエチルマレート等のマレイン酸エステル類;ジブチルフマレートやジエチルフマレート等のフマル酸エステル類;ビニルメチルエーテル、ビニルブチルエーテル及びビニルオクチルエーテル等のビニルエーテル類;アクリロニトリルやメタクリロニトリル等のシアン化ビニル類;エチレン、プロピレン、ブチレン、スチレン等のオレフィン類;イソプレン、ブタジエン等のジエン類;塩化ビニリデン、臭化ビニル等の塩化ビニル以外のハロゲン化ビニリデン、ハロゲン化ビニル類;ジアリルフタレート等のフタル酸アリル類、等が挙げられる。これらのモノマーは、単独で、又は複数種を組み合わせて用いてもよい。
可塑剤としては、塩化ビニル樹脂と相溶性を有するものであれば特に制限はなく、例えば、フタル酸ジブチル(DBP)、フタル酸ジオクチル(DOP)、フタル酸ジイソノニル(DINP)、フタル酸ジイソデシル(DIDP)、フタル酸ジウンデシル(DUP)等のフタル酸系可塑剤;アジピン酸ジブチル等のアジピン酸系可塑剤;リン酸トリブチル、リン酸トリクレジル、リン酸トリフェニル等のリン酸系可塑剤;トリメリット酸トリブチル、トリメリット酸トリオクチル等のトリメリット酸系可塑剤;アジピン酸系ポリエステルなど公知の各種ポリエステル系可塑剤;アセチルトリブチルシトレート、アセチルトリオクチルシトレート等のクエン酸エステル類;等が挙げられる。中でも、透湿度を上記範囲内としやすく、施工適性とともに長期密着性を向上させる観点から、また加工性を向上させる観点から、フタル酸系可塑剤、アジピン酸系可塑剤、ポリエステル系可塑剤が好ましく、フタル酸系可塑剤、ポリエステル系可塑がより好ましい。また、これらの可塑剤は、単独で、又は複数種を組み合わせて用いてもよい。
可塑剤の含有量を上記範囲内とすることで、透湿度を所望の範囲に調整しやすくなり、施工適性とともに長期密着性を向上させることができる。また、可塑剤の含有量を20質量部以上とすることで、塩化ビニル樹脂を柔軟とし、加工性を向上させることができ、一方、50質量部以下であると可塑剤のブリードアウトを抑制し、安定して透湿度を所望の範囲に調整しやすくなり、施工適性とともに長期密着性を向上させることができる。
基材層を着色する場合、基材層中には、染料及び顔料等の着色剤を添加することができる。これら着色剤の中では、退色を抑制しやすい顔料が好ましい。
顔料としては、亜鉛華、鉛白、リトポン、二酸化チタン(チタン白)、沈降性硫酸バリウムおよびバライト等の白色顔料;カーボンブラック、アオメチンアゾ系黒顔料、ペリレン系黒顔料等の黒色顔料;鉛丹、酸化鉄赤、キナクリドンレッド、ポリアゾレッド等の赤色顔料;黄鉛、亜鉛黄(亜鉛黄1種、亜鉛黄2種)、イソインドリノンイエロー、ニッケル-アゾ錯体等の黄色顔料;ウルトラマリン青、プロシア青(フェロシアン化鉄カリ)等の青色顔料;等が挙げられる。
基材層は、化粧シートの他の層や被着材との密着性を高めるために、基材層の片面又は両面に、酸化法、凹凸化法等の物理的表面処理、又は化学的表面処理等の表面処理を施したり、プライマー層を形成したりしてもよい。
表面保護層は、化粧シートの耐擦傷性を良好にする観点から、硬化性樹脂組成物の硬化物を含むことが好ましい。硬化性樹脂組成物の硬化物は表面保護層に含まれる樹脂成分となる。また、表面保護層は樹脂成分以外の成分(例えば、上記一般式(I)~(III)に示すヒドロキシフェニルトリアジン化合物)を含み、硬化性樹脂組成物の硬化物はバインダー樹脂としての役割を有する。
表面保護層を構成する全樹脂成分に対して、硬化性樹脂組成物の硬化物の割合は70質量%以上であることが好ましく、90質量%以上であることがより好ましく、95質量%以上であることがさらに好ましく、100質量%であることがよりさらに好ましい。
すなわち、上記表面保護層用樹脂組成物は、上記硬化性樹脂組成物と、上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、上記一般式(II)又は上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含み、
表面保護層用樹脂組成物における樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、
次の[1]又は[2]を満たすことが好ましい。
[1]紫外線吸収剤として上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(II)に示すヒドロキシフェニルトリアジン化合物とを含有し、
上記一般式(I)に示すヒドロキシフェニルトリアジン化合物の含有量と上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量との合計100質量%に対する、上記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量が50質量%以下である。
[2]紫外線吸収剤として上記一般式(I)に示すヒドロキシフェニルトリアジン化合物と上記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含有する。
上記表面保護層用樹脂組成物を用いることにより、化粧シートを苛酷な環境で使用したとしても、紫外線吸収剤のブリードアウト抑制及び長期耐候性の維持を極めて良好に発現し得る。
また、上記硬化性樹脂組成物には、モノマー成分としてシクロヘキシル(メタ)アクリレートを含有しないことが好ましい。言い換えると、表面保護層は、シクロヘキシル(メタ)アクリレートの硬化物を含有しないことが好ましい。上記硬化性樹脂組成物がシクロヘキシル(メタ)アクリレートをモノマー成分として含有する場合、表面保護層が硬くなり化粧シートの加工性が低下するおそれがあり、該化粧シートを有する化粧材の使用に不都合が生じる場合があることが考えられる。
また、電離放射線とは、電磁波又は荷電粒子線のうち、分子を重合あるいは架橋し得るエネルギー量子を有するものを意味し、通常、紫外線(UV)又は電子線(EB)が用いられるが、その他、X線、γ線などの電磁波、α線、イオン線などの荷電粒子線も含まれる。
電離放射線硬化性化合物は、具体的には、従来電離放射線硬化性樹脂として慣用されている重合性モノマー、重合性オリゴマーの中から適宜選択して用いることができる。
多官能性(メタ)アクリレートモノマーとしては、分子中に2つ以上の電離放射線硬化性官能基を有し、かつ該官能基として少なくとも(メタ)アクリロイル基を有する(メタ)アクリレートモノマーが挙げられる。
加工特性と耐擦傷性及び耐候性を向上させる観点から、多官能性(メタ)アクリレートモノマーの官能基数は2以上8以下が好ましく、2以上6以下がより好ましく、2以上4以下がさらに好ましく、2以上3以下がよりさらに好ましい。これらの多官能性(メタ)アクリレートは、単独で、又は複数種を組み合わせて用いてもよい。
さらに、重合性オリゴマーとしては、他にポリブタジエンオリゴマーの側鎖に(メタ)アクリレート基をもつ疎水性の高いポリブタジエン(メタ)アクリレート系オリゴマー、主鎖にポリシロキサン結合をもつシリコーン(メタ)アクリレート系オリゴマー、小さな分子内に多くの反応性基をもつアミノプラスト樹脂を変性したアミノプラスト樹脂(メタ)アクリレート系オリゴマー、あるいはノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、脂肪族ビニルエーテル、芳香族ビニルエーテル等の分子中にカチオン重合性官能基を有するオリゴマー等がある。
ウレタン(メタ)アクリレートオリゴマーは、例えば、ポリオール及び有機ジイソシアネートとヒドロキシ(メタ)アクリレートとの反応によって得られる。
ウレタン(メタ)アクリレートオリゴマーは、強靭性及び柔軟性の観点から、原料であるポリオールに由来するアルキレン基の炭素数が1~6であることが好ましく、2~4であることがより好ましい。
また、これらの重合性オリゴマーの重量平均分子量は、加工特性と耐擦傷性及び耐候性を向上させる観点から、2,500以上7,500以下が好ましく、3,000以上7,000以下がより好ましく、3,500以上6,000以下がさらに好ましい。本明細書において、重量平均分子量は、GPC分析によって測定され、かつ標準ポリスチレンで換算された平均分子量である。
光重合開始剤としては、アセトフェノン、ベンゾフェノン、α-ヒドロキシアルキルフェノン、ミヒラーケトン、ベンゾイン、ベンジルジメチルケタール、ベンゾイルベンゾエート、α-アシルオキシムエステル、チオキサントン類等から選ばれる1種以上が挙げられる。
また、光重合促進剤は、硬化時の空気による重合阻害を軽減させ硬化速度を速めることができるものであり、例えば、p-ジメチルアミノ安息香酸イソアミルエステル、p-ジメチルアミノ安息香酸エチルエステル等から選ばれる1種以上が挙げられる。
化粧シートは、表面保護層の基材層側の面に接してプライマー層を有することが好ましい。プライマー層によって、基材層と表面保護層との密着性(透明性樹脂層を有する場合は、透明性樹脂層と表面保護層との密着性)が向上し、屋外暴露した際の長期的な層間密着性の確保(いわゆる耐候密着性)及び耐擦傷性を良好にしやすくできる。
化粧シートは、強度を高めるなどの観点から、基材層と表面保護層との間に透明性樹脂層を有していてもよい。化粧シートがプライマー層を有する場合、透明性樹脂層は、基材層とプライマー層との間に位置することが好ましい。また、化粧シートが装飾層を有する場合、装飾層の保護の観点から、透明性樹脂層は、装飾層と表面保護層との間に位置することが好ましい。
透明性樹脂層中のポリオレフィン系樹脂の含有量は、加工適性の観点から、透明性樹脂層の全樹脂成分に対して50質量%以上であることが好ましく、70質量%以上であることがより好ましく、90質量%以上であることがさらに好ましい。
化粧シートは、意匠性を向上させる観点から、化粧シートの任意の箇所に装飾層を有することが好ましい。装飾層を形成する箇所は、装飾層の耐候性を高める観点から、基材層に近い側であることが好ましい。例えば、化粧シートがプライマー層を有する場合、装飾層は、基材層とプライマー層との間に位置することが好ましい。また、化粧シートが透明性樹脂層を有する場合、装飾層は、基材層と透明性樹脂層との間に位置することが好ましい。
装飾層のバインダー樹脂としては特に制限はなく、例えば、ウレタン樹脂、アクリルポリオール、アクリル樹脂、ポリエステル、アミド樹脂、ブチラール樹脂、スチレン樹脂、ウレタン-アクリル共重合体、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-酢酸ビニル-アクリル共重合体、塩素化プロピレン樹脂、ニトロセルロース樹脂、酢酸セルロース樹脂等が挙げられる。また、1液硬化型樹脂、イソシアネート化合物等の硬化剤を伴う2液硬化型樹脂など、種々のタイプの樹脂を用いることができる。
着色剤の含有量は、装飾層を構成する樹脂100質量部に対して、5質量部以上90質量部以下が好ましく、15質量部以上80質量部以下がより好ましく、30質量部以上70質量部以下がさらに好ましい。
装飾層の厚みは、所望の絵柄に応じて適宜選択すればよいが、被着材の地色を隠蔽し、かつ意匠性を向上させる観点から、0.5μm以上20μm以下が好ましく、1μm以上10μm以下がより好ましく、2μm以上5μm以下がさらに好ましい。
化粧シートが透明性樹脂層を有する場合、基材層と透明性樹脂層との間には、両層の密着性を向上するために接着剤層Aを形成することが好ましい。
なお、基材層と透明性樹脂層との間に、さらに装飾層を有する場合、接着剤層Aと装飾層との位置関係は特に限定されない。具体的には、基材層に近い側から装飾層、接着剤層A及び透明性樹脂層をこの順に有していてもよいし、基材層に近い側から接着剤層A、装飾層及び透明性樹脂層をこの順に有していてもよい。
ウレタン系接着剤としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール等の各種ポリオール化合物と、イソシアネート化合物等の硬化剤とを含む2液硬化型ウレタン樹脂を利用した接着剤が挙げられる。
上述した装飾層、接着剤層A、プライマー層及び表面保護層は、各層を形成する組成物を含む塗布液を、グラビア印刷法、バーコート法、ロールコート法、リバースロールコート法、コンマコート法等の公知の方式で塗布し、必要に応じて、乾燥、硬化することにより形成することができる。
また、透明性樹脂層は、例えば、加熱溶融押出しにより形成することができる。
エンボス加工を行う場合、例えば、化粧シートを好ましくは80℃以上260℃以下、より好ましくは85℃以上160℃以下、さらに好ましくは100℃以上140℃以下に加熱し、化粧シートにエンボス版を押圧して、エンボス加工を行うことができる。エンボス版を押圧する箇所は、化粧シートの表面保護層側とすることが好ましい。
本発明の化粧シートは、透湿度が0.75g/m2・24h以上45g/m2・24h以下であることが好ましい。このような透湿度を有することにより、更に施工適性、長期密着性、加工適性、及び耐候性(特に、日光中の紫外線に曝露された際の外観変化の抑制)に優れたものとなる。
具体的には、化粧シートの透湿度を上記範囲内とすることで、施工過程における初期密着強度が向上するので、施工の際に、初期密着強度が不足することにより当該化粧シートの端面が剥がれる、いわゆるスプリングバックの発生を抑制することができるため、施工効率が向上する。かかる初期密着強度の向上効果は、特に、初期接着時に湿気を必要とする、湿気硬化型且つホットメルト型ウレタン樹脂系の接着剤層を介して化粧シートを被着材に貼着した場合に顕著に奏せられる。他方、化粧シートと被着材とを接着剤層を介して化粧材とした場合、主に化粧シートと被着材との間における接着剤層の劣化を抑制することができるので、当該劣化による剥離を抑制し、長期使用しても剥離が生じない、長期密着性を向上させることとなる。すなわち、化粧シートの透湿度を上記範囲とすることで、施工過程における初期密着強度の向上による施工適性の向上とともに、長期使用しても剥離が生じない長期密着性の向上を図ることができる。かかる長期密着強度の向上効果は、特に、湿気による加水分解で劣化する性質のある、湿気硬化型且つホットメルト型ウレタン樹脂等のウレタン樹脂系の接着剤層を介して化粧シートを被着材に貼着した場合に顕著に奏せられる。
なお、透湿度を上記範囲とすることによる長期密着性の効果は、表面保護層において、樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、かつ、表面保護層が上記[1]又は[2]を満たすことにより得られるものである。言い換えると、表面保護層が前述した構成を具備しない場合には、透湿度が上記範囲であったとしても、紫外線の作用で基材及び接着剤層が、樹脂の分子鎖の切断や光化学反応により劣化してしまい、これが接着界面近傍の機械的強度の低下をもたらす他、化粧シートの透湿度の増加を招き、長期密着性を良好にすることはできない。
一方、表面保護層の構成を前述したように最適化したとしても、化粧シートの透湿度が45g/m2・24hを超える場合は、長期密着性の低下以外に、外観上の変化に関する耐候性も低下しやすい。この原因は、「化粧シートの透湿度が高くなるにしたがって、化粧シート中に含まれる紫外線吸収剤の透過性も高くなるため、紫外線吸収剤がブリードアウトしやすくなること」、及び「長期間の屋外曝露に伴い化粧シート中の紫外線吸収剤の減少量が多くなり、化粧シートの紫外線への耐久性が徐々に低下すること」が考えられる。
透湿度の調整は、既述のように、主に基材を構成する材料の種類、樹脂性樹脂層を有する場合は樹脂層を構成する材料の種類等によって行うことができる。
本発明の化粧材は、被着材と上記の本発明の化粧シートとを有するものであり、具体的には、被着材の装飾を要する面と、化粧シートの基材層側の面とを対向させて積層したものである。
被着材としては、後述する各種素材からなる平板、曲面板等の板材;後述する各種素材からなる円柱、多角柱等の立体形状物品;後述する各種素材からなるシート、フィルム等が挙げられる。
各種素材としては、杉、檜、松、ラワン等の各種木材から成る木材単板、木材合板、集成材、パーティクルボード、MDF(中密度繊維板)等の木質繊維板等の木質部材;鉄、アルミニウム、銅、或いはこれら金属の1種以上を含む合金等の金属部材;ガラス、陶磁器等のセラミックス、石膏、セメント、ALC(軽量気泡コンクリート)、珪酸カルシウム系等の非セラミックス窯業系材料等の窯業部材;アクリル樹脂、ポリエステル、ポリスチレン、ポリプロピレン等のポリオレフィン樹脂、ABS(アクリロニトリル-ブタジエン-スチレン共重合体)樹脂、フェノール樹脂、塩化ビニル樹脂、セルロース樹脂、ゴム等の樹脂部材等が挙げられる。また、これらの素材は、単独で、又は複数種を組み合わせて用いることができる。
被着材と化粧シートとは、優れた接着性を得るため、接着剤層Bを介して貼り合わせられることが好ましい。
また、接着剤層には、粘着剤を用いることもできる。粘着剤としては、アクリル系、ウレタン系、シリコーン系、ゴム系等の粘着剤を適宜選択して用いることができる。
化粧材は、化粧シートと被着材とを積層する工程を経て製造することができる。
本工程は、被着材と、本発明の化粧シートとを積層する工程であり、被着材の装飾を要する面と、化粧シートの基材層側の面とを対向させて積層する。被着材と化粧シートとの積層する方法としては、例えば、接着剤層Bを介して化粧シートを板状の被着材に加圧ローラーで加圧して積層するラミネート方法等が挙げられる。
実施例1~14及び比較例1~3で得られた化粧シートについて、下記1-1~1-2の評価を行った。結果を表1~3に示す。
実施例1~14及び比較例1~3で得られた化粧シートについて、1,200時間放置する耐候試験を行った。耐候試験後の化粧材の外観を目視で観察し、以下の基準で評価した。なお、試験装置及び試験条件は下記のとおりである。
1:外観変化は確認されなかった。
2:極軽微な色調変化又は艶変化が確認された。
3:軽微な色調変化又は艶変化が確認された。
4:色調変化又は艶変化が確認された。
5:顕著な色調変化、顕著な艶変化、割れの少なくともいずれかが確認された。
〔試験装置〕
ダイプラ・ウィンテス社製の商品名「ダイプラ・メタルウェザー」
〔照射条件〕
照度:65mW/m2、ブラックパネル温度:63℃、槽内湿度:50%RH、時間:20時間
〔結露条件〕
照度:0mW/m2、槽内湿度:98%RH、時間:4時間
実施例1~14及び比較例1~3で得られた化粧シートを60℃温水の恒温槽に1週間浸漬した後、取り出して十分に乾燥させてから外観を観察し、以下の基準で評価した。
〇:外観の変化が確認されなかった。
△:わずかな膨れや気泡、艶変化、シート成分の析出等の外観変化が確認された。
×:著しい膨れや気泡、艶変化、シート成分の析出等の外観変化が確認された。
[実施例1~14、比較例1~3]
両面コロナ放電処理を施したポリプロピレン樹脂シート(厚さ:60μm)を基材とし、該基材の一方の面に2液硬化型アクリル-ウレタン樹脂をバインダーとし、バインダー樹脂100質量部に対して着色剤を30質量部含有する印刷インキを、グラビア印刷法で塗布して木目模様の装飾層(厚さ:3μm)を設け、他方の面に2液硬化型ウレタン-硝化綿混合樹脂組成物を塗布して裏面プライマー層(厚さ:3μm)を形成した。
装飾層の上に、透明のポリウレタン樹脂系接着剤を塗布して接着剤層(乾燥後の厚さ:3μm)を形成し、透明なポリプロピレン樹脂をTダイ押出機により加熱溶融押出しして、透明性樹脂層(厚さ:80μm)を形成した。
次いで、透明性樹脂層の表面にコロナ放電処理を施した後、ポリカーボネート系ウレタンアクリル共重合体及びアクリルポリオールからなる樹脂成分を含む樹脂組成物を含む塗布液を、グラビア印刷法で塗布してプライマー層(乾燥後の厚さ:4μm)を形成した。
さらに、プライマー層上に、下記の表面保護層用樹脂組成物をロールコート法により塗布して未硬化樹脂層を形成し、電子線(加速電圧:175kV、5Mrad(50kGy))を照射して未硬化樹脂層を硬化させて、表面保護層(厚さ:5μm)を形成した。
次いで表面保護層の上からエンボス加工を実施し、化粧シートを作製した。
3官能のウレタンアクリレートオリゴマー(重量平均分子量約5000、電離放射線硬化性化合物)100質量部に、紫外線吸収剤として前記一般式(I)、一般式(II)及び一般式(III)で表さるヒドロキシフェニルトリアジン化合物を、表1~3に示す割合で加えて、表面保護層用樹脂組成物を調製した。
上記紫外線吸収剤は、次のヒドロキシフェニルトリアジン化合物を用いた。
・紫外線吸収剤1(前記一般式(I)):
[アデカスタブLA-46、株式会社ADEKA製]
・紫外線吸収剤2(前記一般式(II)):
[チヌビン479、チバ・スペシャルティ・ケミカルズ株式会社製]
・紫外線吸収剤3(前記一般式(III)):
[チヌビン1600、チバ・スペシャルティ・ケミカルズ株式会社製]
後述の実施例15~17、比較例4及び参考例1~2で得られた化粧シートについて、下記3-1~3-4の透湿度に関する評価を行った。結果を表4に示す。
実施例15~17、比較例4及び参考例1~2で得られた化粧シートについて、JIS Z0208:1976に規定される防湿包装材料の透湿度試験方法(カップ法)に準拠して、透湿度を測定した。
実施例15~17、比較例4及び参考例1~2で得られた化粧シートと幅25mmの平板上の被着材(材質:ポリ塩化ビニル(PVC))とを、湿気硬化型かつホットメルト型ウレタン樹脂系接着剤(分子中にイソシアネート基を有するポリウレタン系プレポリマー、「1308.20(品名)」、TAKA社製)を120℃で溶融してなる厚さ50μmの接着剤層を介して貼着し、室温23℃にて該接着剤層を冷却し、固化させて、1時間90℃の環境下に放置して試料を作製し、25℃の温度環境下にて、テンシロン万能材料試験機(「テンシロンRTC-1250A(品名)」、オリエンテック(株)製)を用い、引張速度:10mm/分、剥離方向90°、チャック間距離:30mmの条件でピーリング試験を行い、ピーリング強度を初期接着強度として測定し、以下の基準で評価した。B評価以上であれば、施工適性の評価は合格である。
A:ピーリング強度が1.0N/mm以上であった。
B:ピーリング強度が0.5N/mm以上1.0N/mm未満であった。
C:ピーリング強度が0.5N/mm未満であった。
上記「3-2.施工適性の評価」で作製した試料を、70℃90%RHの湿熱環境に6週間放置した後、25℃の温度環境下にて、テンシロン万能材料試験機(「テンシロンRTC-1250A(品名)」、オリエンテック(株)製)を用い、引張速度:50mm/分、剥離方向90°の条件でピーリング試験を行い、ピーリング強度を測定し、以下の基準で評価した。B評価以上であれば、長期密着性の評価は合格である。
A:ピーリング強度が2.0N/mm以上であった。
B:ピーリング強度が1.0N/mm以上2.0N/mm未満であった。
C:ピーリング強度が1.0N/mm未満であった。
上記「3-2.施工適性の評価」で試料を作製において貼着(ラミネート)する際、曲げ部分(曲げ角度:1mmR)における化粧材の浮きを目視にて確認し、以下の基準で評価した。B評価以上であれば、加工適性は合格である。
A:浮きは全く確認されなかった。
B:浮きはほとんど確認されなかった。
C:浮きが確認され、剥離が生じた。
実施例1において、基材層を、ポリプロピレン系樹脂シート(厚さ:80μm、結晶化度:70%、プロピレン-エチレンランダム共重合体(エチレン含有量:4.5質量%以下))とした以外は、実施例1と同様にして実施例15の化粧シートを得た。
実施例1において、基材層を、ポリプロピレン系樹脂シート(厚さ:60μm、結晶化度:50%、プロピレン-エチレンランダム共重合体(エチレン含有量:4.5質量%以下))とした以外は、実施例1と同様にして実施例16の化粧シートを得た。
実施例1において、基材層を、ポリプロピレン系樹脂シート(厚さ:60μm、結晶化度:40%、プロピレン-エチレンランダム共重合体(エチレン含有量:4.5質量%以下))とし、透明性樹脂層の厚さを40μmとした以外は、実施例1と同様にして実施例17の化粧シートを得た。
比較例1において、基材層を、ポリプロピレン系樹脂シート(厚さ:100μm、結晶化度:70%、プロピレン-エチレンランダム共重合体(エチレン含有量:4.5質量%以下))とし、透明性樹脂層の厚さを100μmとした以外は、比較例1と同様にして比較例4の化粧シートを得た。
比較例1において、基材層を、ポリ塩化ビニル樹脂シート(厚さ:120μm、ポリ塩化ビニル樹脂100質量部に対して、可塑剤としてポリエステル系可塑剤(アジピン酸系ポリエステル)を33質量部加えた樹脂組成物を押出し成形して作製したものである。)とし、接着剤層A及び透明性樹脂層を設けなかった以外は、比較例1と同様にして参考例1の化粧シートを得た。
比較例1において、基材層を、ポリ塩化ビニル樹脂シート(厚さ:120μm、ポリ塩化ビニル樹脂100質量部に対して、可塑剤としてフタル酸エステル系可塑剤(フタル酸ウンデシル(DUP))を38質量部加えた樹脂組成物を押出し成形して作製したものである。)とし、接着剤層A及び透明性樹脂層を設けなかった以外は、比較例1と同様にして参考例2の化粧シートを得た。
なお、表中には示していないが、実施例15~17の長期耐候性及びブリードアウトに関する評価は、実施例1と同等であった。また、比較例4の長期耐候性及びブリードアウトに関する評価は、比較例1と同等であった。
10:表面保護層
20:プライマー層
30:透明性樹脂層
40:装飾層
50:基材層
Claims (10)
- 少なくとも基材層及び表面保護層を有する化粧シートであって、
前記表面保護層において、樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、
前記表面保護層が次の[1]又は[2]を満たす、化粧シート。
[1]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物とを含有し、
下記一般式(I)に示すヒドロキシフェニルトリアジン化合物の含有量と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量との合計100質量%に対する、下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量が50質量%以下である。
[2]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含有する。
- 前記基材層と前記表面保護層との間に、装飾層、透明性樹脂層及びプライマー層から選ばれる一以上の層を有する、請求項1に記載の化粧シート。
- 前記表面保護層が硬化性樹脂組成物の硬化物を含む、請求項1又は2に記載の化粧シート。
- 前記基材層がオレフィン系樹脂を含む、請求項1~3の何れか1項に記載の化粧シート。
- JIS Z0208:1976に規定される防湿包装材料の透湿度試験方法(カップ法)に準拠して測定された透湿度が0.75g/m2・24h以上45g/m2・24h以下である、請求項1~4の何れか1項に記載の化粧シート。
- 被着材と請求項1~5の何れか1項に記載の化粧シートとを有する化粧材。
- 前記化粧シートと前記被着材との間に、ウレタン系接着剤で構成される接着剤層を有する請求項6に記載の化粧材。
- 前記ウレタン系接着剤が、湿気硬化型接着剤である請求項7に記載の化粧材。
- 前記被着材が、金属部材又は樹脂部材である請求項6~8の何れか1項に記載の化粧材。
- 硬化性樹脂組成物と、下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と、下記一般式(II)又は下記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含む、表面保護層用樹脂組成物であり、
前記表面保護層用樹脂組成物における樹脂100質量部に対する全紫外線吸収剤の含有量が10質量部以下であり、
次の[1]又は[2]を満たす、表面保護層用樹脂組成物。
[1]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物とを含有し、
下記一般式(I)に示すヒドロキシフェニルトリアジン化合物の含有量と下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量との合計100質量%に対する、下記一般式(II)に示すヒドロキシフェニルトリアジン化合物の含有量が50質量%以下である。
[2]紫外線吸収剤として下記一般式(I)に示すヒドロキシフェニルトリアジン化合物と下記一般式(III)に示すヒドロキシフェニルトリアジン化合物とを含有する。
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EP (1) | EP3950335B1 (ja) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022210875A1 (ja) * | 2021-03-31 | 2022-10-06 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧部材 |
JP2022159108A (ja) * | 2021-03-31 | 2022-10-17 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧部材 |
WO2023190538A1 (ja) * | 2022-03-28 | 2023-10-05 | 大日本印刷株式会社 | 化粧シート及び化粧材 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006501339A (ja) * | 2002-10-02 | 2006-01-12 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Uv吸収剤の相乗的組合せ |
JP2006307142A (ja) * | 2005-03-31 | 2006-11-09 | Dainippon Printing Co Ltd | 耐候剤組成物 |
JP2008535700A (ja) * | 2005-04-13 | 2008-09-04 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | 紫外線安定化成形ポリカーボネート製品 |
JP2013537176A (ja) * | 2010-09-14 | 2013-09-30 | ビーエーエスエフ ソシエタス・ヨーロピア | 特定のビス(ビフェニル)トリアジン誘導体及びその混合物の紫外線吸収剤としての使用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5196042B2 (ja) * | 2005-03-31 | 2013-05-15 | 大日本印刷株式会社 | 化粧シート |
JP5540589B2 (ja) * | 2009-07-08 | 2014-07-02 | 株式会社トッパン・コスモ | 化粧シート |
WO2015165871A1 (en) * | 2014-04-29 | 2015-11-05 | Basf Se | Multi-layered film and the use thereof |
KR102427913B1 (ko) * | 2015-04-03 | 2022-08-01 | 주식회사 쿠라레 | 수지 조성물 및 그 제조 방법, 성형체, 필름 그리고 물품 |
JP6556050B2 (ja) * | 2015-12-25 | 2019-08-07 | ヘンケルジャパン株式会社 | 湿気硬化型ホットメルト接着剤 |
JP6977294B2 (ja) * | 2017-03-31 | 2021-12-08 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧材 |
KR20210021541A (ko) * | 2018-06-21 | 2021-02-26 | 도판 인사츠 가부시키가이샤 | 보호 필름 및 시트 |
-
2020
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- 2020-03-30 CN CN202080034070.2A patent/CN113795381B/zh active Active
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- 2020-03-30 AU AU2020251539A patent/AU2020251539B2/en active Active
- 2020-03-30 WO PCT/JP2020/014501 patent/WO2020203957A1/ja unknown
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006501339A (ja) * | 2002-10-02 | 2006-01-12 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Uv吸収剤の相乗的組合せ |
JP2006307142A (ja) * | 2005-03-31 | 2006-11-09 | Dainippon Printing Co Ltd | 耐候剤組成物 |
JP2008535700A (ja) * | 2005-04-13 | 2008-09-04 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | 紫外線安定化成形ポリカーボネート製品 |
JP2013537176A (ja) * | 2010-09-14 | 2013-09-30 | ビーエーエスエフ ソシエタス・ヨーロピア | 特定のビス(ビフェニル)トリアジン誘導体及びその混合物の紫外線吸収剤としての使用 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022210875A1 (ja) * | 2021-03-31 | 2022-10-06 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧部材 |
JP2022159108A (ja) * | 2021-03-31 | 2022-10-17 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧部材 |
JP7324436B2 (ja) | 2021-03-31 | 2023-08-10 | 大日本印刷株式会社 | 化粧シート及びこれを用いた化粧部材 |
WO2023190538A1 (ja) * | 2022-03-28 | 2023-10-05 | 大日本印刷株式会社 | 化粧シート及び化粧材 |
JP7392023B2 (ja) | 2022-03-28 | 2023-12-05 | 大日本印刷株式会社 | 化粧シート及び化粧材 |
Also Published As
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EP3950335A1 (en) | 2022-02-09 |
AU2020251539A1 (en) | 2021-11-18 |
JPWO2020203957A1 (ja) | 2021-12-02 |
AU2020251539B2 (en) | 2023-03-30 |
EP3950335B1 (en) | 2023-09-20 |
US20220186004A1 (en) | 2022-06-16 |
EP3950335A4 (en) | 2022-12-28 |
JP6969704B2 (ja) | 2021-11-24 |
CN113795381A (zh) | 2021-12-14 |
CN113795381B (zh) | 2023-11-03 |
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